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Showing papers in "Transactions of The Faraday Society in 1960"




Journal ArticleDOI
TL;DR: In this article, the effects of solute-solvent interactions on the frequencies, intensities and shapes of the infra-red absorption bands of dissolved molecules are discussed and the interaction potential energy U between a single solute molecule and its environment is treated as a variable depending upon the solvent configuration and on the normal co-ordinates of the isolated vibrating solute.
Abstract: The effects of solute-solvent interactions on the frequencies, intensities and shapes of the infra-red absorption bands of dissolved molecules are discussed The interaction potential energy U between a single solute molecule and its environment is treated as a variable depending upon the solvent configuration and on the normal co-ordinates of the isolated vibrating solute Formulae relating the mean solvent shifts Δω to the derivatives of U with respect to the normal co-ordinates and to the anharmonic constants of the free solute are deduced for diatomic and polyatomic molecules Invariants on isotopic substitution, such as Δω/ω, are discussed and it is shown that the effects of isotopic changes on the solvent shift, and hence on the probability of a particular solvent configuration occurring, are normally small The different solvent environments around ground-state and excited-state solute molecules are found to lead to a small difference between the displacements of the Stokes and anti-Stokes lines in the Raman spectra of dissolved substances; the difference has not yet been established experimentally, and it may prove hard to measure, as it is proportional to the square of the half-width of the band, and is therefore only appreciable when the band is broad

263 citations